US3907321A

US3907321A - Novel tobacco product comprising one or more isomers of an octahydrotetramethyl acetonaphthone

Info

Publication number: US3907321A
Application number: US529087A
Authority: US
Inventors: John B Hall; James Milton Sanders
Original assignee: International Flavors and Fragrances Inc
Current assignee: International Flavors and Fragrances Inc
Priority date: 1974-01-21
Filing date: 1974-12-03
Publication date: 1975-09-23
Anticipated expiration: 1992-09-23

Abstract

Products produced by the process comprising reacting myrcene with 3-methyl-3-pentene-2-one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said DielsAlder adduct with an acid cyclizing agent, in particular, the isomer having the structure:

(WHEREIN THE DASHED LINES REPRESENT METHYL GROUPS ''''CIS'''' TO ONE ANOTHER) HAVE BEEN DISCOVERED TO BE USEFUL FOR MODIFYING THE FRAGRANCE AND AROMA OF SMOKING ARTICLE SIDE STREAMS AND MAIN STREAMS, IMPARTING SWEET, SPICY, SANDALWOOD-LIKE, CEDARWOOD-LIKE AROMAS TO SUCH MAIN STREAMS AND SIDE STREAMS.

Description

United States Patent [191 [111 3,907,321

Hall et al. Sept. 23, 1975 NOVEL TOBACCO PRODUCT COMPRISING Primary Examiner-Melvin D. Rein ONE OR MORE ISOMERS OF AN OCTAHYDROTETRAMETI-IYL ACETONAPIITHONE Inventors: John B. Hall, Rumson; James Milton Sanders, Eatontown, both of NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, N.Y.

Filed: Dec. 3, 1974 Appl. No.: 529,087

Related U.S. Application Data Attorney, Agent, or FirmArthur L. Liberman, Esq.; Harold Haidt, Esq.

[57] ABSTRACT Products produced by the process comprising reacting myrcene with 3-methyl-3-pentene-2-one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said Diels-Alder adduct with an acid cyclizing agent, in particular, the isomer having the structure:

[52] U.S. Cl 131/17 R; 131/144; 260/488 [51] Int. Cl. A24B 15/04 [58] Field of Search 131/2,l5,17,144; 260/488, 343.2

(wherein the dashed lines represent methyl groups [56] References C'ted cis to one another) have been discovered to be use- U ED ST TES PATE ful for modifying the fragrance and aroma of smoking 2,933,506 4/1960 Obloff et al 260/343.2 r i side streams n m in m i p ng 2,978,365 4/1961 Schumacher 131/17 R sweet, spicy, sandalwood-like, cedarwood-like aromas 3.047.433 7/1962 Ba ley et al. 131/17 R to such main streams and side streams. 3,076,022 1/1963 Kitchens 260/488 3 Claims, 6 Drawing Figures LIJ o E. /SOLVENT SIGNAL I (cum, g l .1 I000 Hz SWEEP WIDTH l N M al 5, I

1050 9.50 8.50 7.50 6.50 5.50 4.50 3.50 2.50 1.50 0.5 PPM PEAK 1 FROM EXAMPLEJI AND MAJOR PEAK FROM EXAWLE IE.

US Patent Sept. 23,1975 Sheet 1 of6 3,907,321

2mm m6 Om Omd on m Omf Om m Omd Om N Omd

US Patent Sept. 23,1975 Sheet 3 of6 3,907,321

F I G .3 MAJOR PEAK FROM EXAMPLE I INTENSITY I800 I700 I600 I500 I400 NOVEL TOBACCO PRODUCT COMPRISING ONE OR MORE ISOMERS OF AN OCTAHYDROTETRAMETHYL ACETONAPHTl-IONE This application is a continuation-in-part of copending application for US. patent Ser. No. 434,948 filed on Jan. 21, 1974 which is, in turn, a continuation-inpart of application for US. patent Ser. No. 336,172 filed on Feb. 27, 1973, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to novel tobacco products, novel tobacco flavoring compositions; and processes for producing same, and has for an object the provision of a composition and process for improving the flavor and aroma of tobacco and tobacco smoke.

It is well known in the tobacco art, that the flavor and aroma of the tobacco product and the smoke from the tobacco are very important considerations insofar as the ultimate consumer is concerned. Considerable efforts have been and are being exerted by the manufacturers of tobacco products to provide a product that will be acceptable to the consumer, particularly as regards flavor and aroma characteristics. It has been the common practice in the tobacco industry to prepare blends of domestic and oriental tobaccos in order to provide smoking tobacco which has a pleasing flavor and aroma before and during smoking. However, such a procedure is costly and may at times become prohibitive in the event that certain types of tobacco may be in short supply. Accordingly, there has been considerable work relating to substances which can be used to impart flavors to various tobacco blends. These substances are used to supplement natural materials some of which, as stated above, may be in short supply, and to provide more uniform properties to the finished product.

Sweet, spicy, sandalwood-like and cedarwood-like notes are particularly desirable for many uses concerning the flavoring of tobacco products; both prior to and on smoking.

The isomer mixtures and specific isomer used in our invention have also been found to modify the smoke side stream and main stream of smoking articles by imparting a sweet, spicy, sandalwood-like and cedarwood-like aroma to such side streams and main streams. Materials having such properties have been widely sought after in the past but no such materials which are easily available and have relatively low cost have heretofore been discovered. The prior art contains several disclosures of fragrance uses of compounds having structures similar to compounds contained in the isomer mixtures of our invention and to the specific isomer of our invention.

This invention relates to the utilization of synthetic amber-like fragrance ingredients for fragrancing the side streams and main streams of smoking articles containing tobacco. The materials used in this invention include octahydro-2',3',8',8'-tetramethyl-(2' or 3')- acetonaphthones in which a majority of said acetonaphthones contains the double bond in the 9-10 position, and, in addition, a novel isomer of octahydrotetramethyl acetonaphthone having the structure:

wherein the dashed lines represent methyl groups cis" to one another. The invention also covers processes for.

producing isomer mixtures of octahydro-2,3 ,8 ,8 -tetramethyl-(Z' or 3)acetonaphthone having the generic structure,

Such a generic structure includes individually compounds having an acetyl group at the 2' position, compounds having an acetyl group at the 3' position and mixtures of such compounds. The generic structures set forth above are also intended to include geometric isomers wherein the acetyl group is cis to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety and where the acetyl group is trans to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety. The processes of our invention give rise to isomer mixtures containing the above-named isomers as well as the isomer having the structure:

Briefly, the mixture useful in our invention are produced by means of a two-step reaction:

1. Reacting myrcene with 3-methyl-3-penten-2-one either: a. In the presence of a Lewis acid at temperatures in the range of from 0 up to 50C thereby producing amixture of geometric isomers which are 3 Diels-Alder adducts which are alkenyl acetyl dimethyl substituted cyclohexenes represented by the structure:

b. Reacting myrcene with 3-methyl-3-penten-2-one without using a catalyst at temperatures in the range of 120 up to 180C forming a mixture of isomers (including geometric isomers) of alkenyl acetyl dimethyl substituted cyclohexenes having the generic structure:

2. Cyclizing the resulting substituted cyclohexenes (Diels-Alder adducts) by means of heating same in the presence of phosphoric acid or dilute sulfuric acid (5080%) or boron trifluoride or complexes thereof, e.g., boron trifluoride etherate.

The isomer mixtures produced thusly can be further separated by standard physical separation techniques (e.g., chromatographic techniques as set forth in Example XIV) or standard chemical techniques (e.g., oximation as set forth in Example X1) or they can themselves be incorporated into tobacco or tobacco flavors. It has been found that the novel materials of this invention have persistent fragrances more fully described below which adapts them for incorporation into tobacco or tobacco flavors where it is desired to modify aromas of the main stream and side streams of a smoking article on smoking by imparting to the aroma of such main stream and side stream, sweet, spicy, cedarwood-like notes.

In the first of the two reactions of the process for preparing the materials useful in our invention, myrcene and 3-methyl-3-penten-2-one are the reactants. Myrcene is generally available at purities of 70 percent and upwards and it can be used in this form. It is generally preferred in the practice of this invention to use commercial myrcene (approximately 77 percent purity) although, obviously, purified myrcene may be used. Such a purification is readily accomplished by fractional distillation. The initial reaction may be a thermal Diels- Alder reaction without the use of a Lewis acid catalyst.

at a temperature in the range of 120-180C. Preferably, but not necessarily, an antioxidant and polymerization inhibitor such as the mixture of beta-naphthylamine and pyrogallol may be utilized, as set forth in Example V of British Pat. No. 896,039. Upon performing the first step of the process for preparing the materials useful in our invention by carrying out a thermal Diels- Alder reaction without the use of a Lewis-acid catalyst, the resulting material will be a mixture of approximately 70 weight percent:

and 30 weight percent:

with unknown ratios of geometric cis-trans isomers of each. Where the initial Diels-Alder reaction is carried out using a Lewis acid catalyst, primarily geometric isomers having one basic structure are obtained, to

wit:

Suitable Lewis acid catalysts are aluminum chloride, stannic chloride, titanium tetrachloride, boron trifluoride, and boron trifluoride complexes such as boron trifluoride etherates. The Lewis acid catalyst concentration workable in our process is from 0.5 up to mole percent based on 3-methyl-3-penten-2-one with the preferred range being 38 mole percent. When using the Lewis acid catalyst, it is preferred that a solvent be used and suitable solvents are toluene, benzene and inert chlorinated hydrocarbon solvents such as chloroform and methylene chloride since they do not take part in the reaction. When using a Lewis acid catalyst, the first reaction is operated at a temperature in the range of 0 up to 50C, preferably 3550C. In both the thermal and catalytic Diels-Alder reactions, the mole ratio of myrcene to 3-methyl-3-penten-2-one may be varied from 1:3 to 3:1 or even higher, since the excess reagent may be recovered substantially quantitatively. However, for efficiency and economy as to time, the preferred mole ratio is from 1.111 up to 1.211. The reagents and catalyst may be mixed in any order, however, it is preferred to sequentially add 3-methyl-3- penten-2-one and myrcene to a premix of the catalyst and solvent, the use of solvent in this reaction being preferred also.

The next reaction, following the Diels-Alder reaction, namely cyclization of the acetyl cyclohexene derivative (the Diels-Alder adduct), is accomplished by heating the cyclohexene derivative preferably with a mixture of an acid such as phosphoric acid, diluted sulfuric acid, boron trifluoride or boron trifluoride etherate in the presence of a solvent. The amount of acid cyclization agent may vary from 10 up to 100 weight percent based on the weight of the cyclohexene derivative to be cyclized. Preferably, the weight percent of acid should be between 40 and 50 weight percent. Preferably, an inert solvent having a boiling point at or about the desired reaction temperature is used in the cyclization reaction. The reaction temperature may be anywhere between 25C and the reflux temperature of the reaction mixture. The preferred reaction temperature range is between 95and 115C and accordingly toluene is the preferred solvent since its boiling point at atmospheric pressure is 110C. The quantity of solvent used in the cyclization reaction may vary from 0 weight percent up to 100 weight percent based on the amount of cyclohexene derivative being cyclized. It is preferred to use approximately 50 weight percent of solvent. In the cyclization reaction, the order of mixing reagents and solvents is not critical.

The length of time and temperature of the cyclization reaction will determine the percentage of the geometric isomers having the basic structure:

as compared with the geometric isomers having the other possible basic structures, namely:

"and

Periods of time of the order of 5-7 hours at temperatures of 7080C will yield a mixture wherein isomers having the basic structure (I) will be produced in a quantity of about 80-85 percent, the remaining isomers having the basic structures (II), (III) and (IV). However, if the cyclization reaction is run for a period of time of approximately 10 hours and at 80C greater than 96 percent of the reaction product has a geometric isomer mixture having the basic structure (I). A temperature of reaction of l 15C coupled with a time of reaction of 4 hours will also yield a geometric isomer mixture more than 96 percent of the compounds of which have the basic structure (I). A time of reaction of 6 hours coupled with a reaction temperature of 1 15C will give rise to a reaction product wherein more than 99 percent of the geometric isomers have the basic structure (I).

In the event that the first reaction, the Diels-Alder reaction, is carried out using a Lewis acid catalyst, the mixture of isomers produced as a result of carrying out the second cyclization reaction on the resulting Diels- Alder reaction product has been found to contain a predominant quantity of an isomer having the structure:

Chromatographic techniques can then be effectively utilized to separate, this novel isomer from the cyclization reaction mixture and such a technique is illustrated in Example XIV, infra. This novel isomer has a characteristac intense fruity-amber note. The above isomers are distinguishable from one another by examination of their respective NMR, infrared, and Raman spectra. The fact that the isomers indicated by formulae 1 and V have a tetrasubstituted double bond, and the isomers indicated by formulae II, III and IV have a double bond which is only trisubstituted and not tetrasubstituted is apparent from a study of FIGS. 1-6

The two foregoing reactions may be performed in separate reaction vessels or, more preferably, they may be performed in the same reaction vessel whereby the Diels-Alder reaction and subsequent cyclization steps are carried out without isolating the intermediate Diels- Alder adduct, the cyclohexene derivative. Accordingly, when the Diels-Alder reaction is complete, the desired amount of acid is added without any additional solvents, and the reaction mixture is then stirred at the desired temperature until cyclization is complete.

When the cyclization reaction is subsequently complete, the reaction mass is then washed and the organic layer is separated and distilled.

The distilled product may be used as is or it may be further purified by using gas chromatography tech- 7 niques and/or oximation (see Example IX) followed by recovery of the purified reaction product from the oxime.

The reaction product mixtures as well as the specific isomer of our invention are clear liquids with intense and persistent unique amber and fruity-amber odors. The isomer mixtures as well as the novel specific isomer of our invention are particularly suited to use in tobacco and tobacco flavors as modifiers of the aromas of the main stream and side stream of the smoke created on smoking articles containing said tobacco. They are adapted to modifying tobacco smoke aromas where sweet, spicy, sandalwood-like and cedarwood-like aromas are required in the smoke main stream and side stream.

Furthermore, it has been found that the tobacco additives of our invention when incorporated into tobacco products impart a flavor and aroma both before and during smoking which many smokers consider to be desirable in smoking products. However, it is pointed out that the methods for defining or characterizing the quality of a flavor or aroma in the tobacco art are almost purely subjective and different smokers may define the same flavor quite differently. The compositions of matter comprehended by this invention, by subjective tests, impart characteristic flavors which are desirable in tobacco products and the smoke therefrom even through the exact character thereof cannot be described on the basis of known standards.

In accordance with this invention, one or more of the isomeric mixtures of octahydrotetramethyl acetonaphthones or the specific isomer thereof is added to tobacco or applied to a smoking article or its component parts in amounts of about lO-5,000 parts per million (ppm) based on dry weight of the tobacco product. Preferably, the amount of additive is between about 200 and 2,000 ppm by weight in order to provide a tobacco product having a desired flavor and aroma. However, the amount used will depend upon the amount of flavor and aroma desired and the particular compound or mixture thereof that is used. The additive may be incorporated at any step in the treatment of the tobacco but is preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes. Likewise, it will be apparent that only a portion of the tobacco need be treated and the thus treated tobacco may be blended with other tobaccos before the cigarettes or other smoking articles are formed. In such case the tobacco treated may have the additive in excess of the amounts above indicated so that when blended with other tobaccos the final product will have the percentage within the indicated range.

In accordance with one specific embodiment of this invention, an aged, flue-cured and shredded tobacco is sprayed with a 1 percent ethyl alcohol solution of a compound having the structure:

in an amount to provide a tobacco containing 400 ppm by weight of the additive on a dry basis. Thereafter, the

8 alcohol is removed by evaporation and the tobacco is manufactured in'to cigarettes by the usual techniques. It has been found that the cigarette when prepared as indicated has a desired and pleasing flavor, an aroma which to some people is described as sweet, spicy, sandalwood-like and cedarwood-like and is detectable and pleasing in the main and side smoke streams when the cigarette is smoked.

The additives falling within the scope of this invention may be applied to the tobacco by spraying, dipping or otherwise utilizing suitable suspensions or solutions of the additive. Thus water or volatile organic solvents, such as alcohol, ether, acetone, volatile hydrocarbons and the like, may be used as the carrying medium for the additive while it is being applied to the tobacco. Also, other flavor-and-aroma-producing additives, such as:

a. Esters, for example:

Ethyl butyrate; Ethyl acetate; Ethyl valerate; Amyl acetate; Phenyl ethyl isovalerate; and Methyl heptynyl carbonate b. Aldehydes, for example:

3-phenyl-2-pentenal; 3-phenyl-3-pentenal; Phenyl acetaldehyde; Cinnamaldehyde; and Beta-ethyl-cinnamaldehyde c. Ketones, for example:

Benzylidene acetone; Acetophenone; Maltol; and Ethyl maltol d. Acetals, for example:

3-phenyl-4-pentenal dimethyl acetal; and 3-phenyl-4-pentenal diethyl acetal (described in copending application for US. patent Ser. No. 276,922 filed on Aug. 1, 1972) e. Natural oils and extracts, for example:

Vanilla; Coffee extract; Origanum oil; Cocoa extract; Oil of cloves; Nutmeg oil; Celery seed oil; Bergamot oil; and Ylang-ylang oil f. Lactones, for example:

Delta-decalactone; Delta-undecalactone; Delta-dodecalactone; Gamma-undecalactone; and Coumarin g. Ethers, for example:

Dibenzyl ether; Vanillin; and Eugenol h. Pyrazines, for example:

2-Acetyl pyrazine; 2-Acetyl-6-methyl pyrazine; 2-Ethyl pyrazine; 2,3-Dimethyl pyrazine; 2,5-Dimethyl pyrazine; and Z-Ethyl-S-methyl pyrazine i. Pyrroles, for example:

9 N-cyclopropyl pyrrole; and N-cyclooctyl pyrrole as well as those additives disclosed in U.S. Pat. Nos. 2,766,145; 2,905,575; 2,905,576; 2,978,365; 3,041,211; 2,766,149; 2,766,150; 3,589,372; 3,288,146; 3,402,051; and 3,380,457 as well as Australian Pat. Nos. 444,545; 444,507; and 444,389 may be incorporated into the tobacco with the additives of this invention.

While this invention is principally useful in the manufacture of cigarette tobacco, it is also suitable for use in connection with the manufacture of pipe tobacco, cigars or other tobacco products. Furthermore, the compounds may be added to certain tobacco substitutes of natural or synthetic origin.

Also, the invention has been particularly described with reference to the addition of the compounds directly to tobacco. However, it will be apparent that the compound may be applied to the paper of the cigarette or to the wrapper of a cigar. Also, it may be incorporated into the filter tip, the packaging material or the seam paste employed for gluing the cigarette paper. Thus, a tobacco product is provided which includes the specified additives and tobacco although in every instance the compound need not be admixed with the tobacco as above specifically described.

In the accompanying drawings forming part of this application, the figures which represent charts referred to in the above examples are listed as follows:

FIG. 1 is a chart showing the nuclear magnetic resonance spectrum of peak No. 1 trapped by gas chromatography techniques from the product produced by the process of Example II, or the major peak trapped by gas chromatography techniques from the product of Example VI.

FIG. 2 is a chart showing the nuclear magnetic resonance spectrum of peak No. 2 trapped by gas chromatography techniques from the material produced by the process of Example II.

FIG. 3 is a portion of the Raman spectrum of the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VI.

FIG. 4 is an infrared analysis spectrum of the material which is the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VI.

FIG. 5 is a nuclear magnetic resonance spectrum of the material produced according to the process of Example XI.

FIG. 6 is the nuclear magnetic resonance spectrum of the product produced according to the process of Example IX.

The following Examples I-XI are given to illustrate methods for producing products found to be useful in .the practice of our invention.

Chemical Shifts (Note 1) 10 The following Examples XII-XIV are given to illustrate the embodiments of the invention as it is presently preferred to practice it. It will be understood that these examples are illustrative and the invention is not to be 5 considered as restricted thereto except as indicated in the appended claims.

EXAMPLE I toluene 5 3-Methyl-3-pentenone (2060 g, 95 percent) is added in 15 minutes to a suspension of aluminum chloride (90 g) in toluene (2 kg). The initial exotherm dies out after approximately 5 percent of the 3-methyl-3-pentenone is added. The mass is warmed to C, and myrcene (3530 g, 77 percent) was added over a period of 2 hours with external cooling as needed to maintain the reaction mixture at 35-40C. The mixture is stirred at 3540C for 2 hours, 27 g aluminum chloride is added, and the mass is stirred an additional 9 hours at 3540C.

After standing overnight at room temperature, the mixture is washed at C with 10 percent sodium chloride solution and 15 percent sodium sulfate solution. The washed organic solution is mixed with 100 g triethanolamine, 100 g Primol (U.S.P. white mineral oil available from Exon Incorporated of Linden, New J ersey) and 5 g Iono (registered trademark of the Shell Chemical Company; butylated hydroxy toluene) and is distilled rapidly at 2-3.5 mm Hg using a short column to give 3999 g of product, bp l46150C/23.5 mm Hg.

IR analysis (Peaks): 2962, 2904, 2840, 1698, 1450, 14301380,l373,1351,l222,1195,11601138,1098, 1090, 1080 cm.

NMR analysis (100 MH CDCl Interpretation v -continued Chemical Shifts (Note 1) lnterpretation l.772.50 8(9H, mult.) [-1 E H H u d *1 2.06 5(3H, sing.) )Ok H3 L62 6(3H. sing.) CH 1.54 8(3H, sing.)

0.92 8(3H, Sing.) 0 Ea 0.76 6(3H, doublet) O Note I All nuclear magnetic resonance chemical shifts are reported in parts per million relative to tetramethylsilane.

Mass Spectral Analysis: m/e 234 (M'), 191, 123, 121,106, 69, 43, 4l.

EXAMPLE ll H PO The product of Example I (3 kg, 98.7 percent) is added over a period of minutes to a well-stirred mixture of 1.5 kg of toluene and 1.5 kg of percent phosphoric acid maintained at 70-80C. The mixture is stirred vigorously at 7080C for 5.5 hours and then is cooled and mixed with 3 kg of crushed ice. The organic phase is subsequently washed with 10 percent sodium chloride solution, 10 percent sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is mixed with triethanolamine g), Primol (50 g) and lonol (3 g) and is rapidly distilled under reduced pressure using a short column.

Fractionation of the crude product gives 2,604 g of a mixture of geometric isomers (bp l34l35C/2.8 mm Hg) having an intense amber aroma.

Using GLC analysis, this material shows two major peaks (Varian Aerograph model 200, 10' X A, 5 percent Carbowax K 20 M on chromosorb G, helium flow 3,907,321 0 "r3 14 rate 80 cc per minute, temperature programmed quite different. The NMR analysis for Peak 1 is set l0O-200C at l0C/min.), Peak 1 93 percent, Peak forth in Table 1 and is as follows:

Table 1 Chemical Shifts Interpretation 2.16 8(3H, singlet) )0 E: 1.00 8(3, singlet) H C CH CH 0.98 awn, singlet) Q and 0.81 8(3H, doublet, J=6cps) 0 C H H 3 0.6l2.568( 1 lH,multiplet) 2 7 percent. Peaks 1 and 2 are trapped from the The NMR analysis for Peak 2 is set forth in Table 2 above column. The NMR spectra of the two peaks are and is as follows:

Table 2 Chemical Shifts Interpretation 5.32 8( 1H, broad multiplet) 2.1 l 5(3H, singlet Table 2-continued Chemical Shifts Interpretation 0.89 awn. singlet) H 3 0.70 8(3H, doublet, J=4cps) 0.65-2.10 8(10H, multiplet) and/or Peak 1 has a slight buttery note with a strong woody amber character. Peak 2 is weak, low keyed with a green vegetable character.

IR analysis for Peak 1: 2950, 2922, 1702, 1455, 1440, 1382, 1359, 1235, 1196, 1178, 1159, 1120, 1103, 1092, 1083, 956cm".

Mass spectral analysis for Peak 1: m/e 234 (M*), 219,191, 188,186,161, 149,147,135, 133, 121,119, 109,107, 105,95,93,92, 83, 81,79,77,69,67,55,43,

Generic structure of isomers of mixture of Peak 1: 6O EXAMPLE I" Into a 2 liter reaction vessel equipped with stirrer, thermometer and reflux condenser, the following ingredients are placed:

400 grams Myrcene (77 percent) 17 228 grams 86.1 percent 3-Methyl-3-pentene- 2-one 1 gram lonol (Registered trademark of the Shell Chemical Co.) (Butylated l-lydroxy Toluene) 50 grams Toluene The reaction vessel is operated at atmospheric pressure EXAMPLE IV The Diels-Alder product of Example Ill is added over a period of 45 minutes to a well-stirred mixture of 100 grams toluene and 100 grams 62 percent sulfuric acid maintained at 7080C. The mixture is stirred vigorously at 70-80C for 6 hours and is then cooled and mixed with l kilogram of crushed ice. The organic phase is subsequently washed with 10 percent sodium chloride solution, 10 percent sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is then mixed with triethanolamine g), Primol (5 g) and Ionol (l g) and is rapidly distilled under reduced pressure using a short column. In this way, a product is obtained containing only traces of uncyclized starting material and containing geometric isomers having the basic generic structure:

EXAMPLE V Into a 2 liter reaction flask equipped with reflux condenser, stirrer and thermometer, the following ingredients are placed:

500 grams Diels Alder adduct mixture prepared according to the process of Example III 250 grams 85 percent phosphoric acid 250 grams Toluene The reaction mass is heated to reflux at atmospheric pressure l 18C) and maintained at reflux for a period of 3 /2 hours after which time the reaction mass was cooled down. The reaction mass is then washed with one 1 liter portion of water; then two 500 cc portions of water; then one 500 cc portion of 5 percent sodium carbonate and finally one 500 cc portion of saturated sodium chloride. The washed reaction mass is then thereby gradually increasing the pot temperature to 18 stripped of solvent thereby. giving rise to 445 grams of crude product. The crude product is then rushed over and distilled through a fractionation column after adding to it, 2 grams of calcium carbonate, 30 grams of Primol and 1 gram of Ionol, at a vapor temperature of 124-l26C and 2.1-2.8 mm Hg. pressure.

IR, NMR and mass spectral analyses yield the information that the resultant product is a mixture of geometric isomers having chemical structures, percent of which have the generic structure:

and 30 percent of which have the generic structure:

whereinone of the wavy lines in each of the above structures is a carbon-carbon double bond and the other of the wavy lines in each of the above structures represents a carbon-carbon single bond.

EXAMPLE VI In situ preparation of l',2',3,4',5,6,7,8'-octahydro-2',3',8,8'-tetramethyl-2'-acetonaphtone isomer mixture from myrcene and 3-methyl-3-pentene-2-one Into a 5 liter reaction flask equipped with stirrer, reflux condenser, addition funnel and thermometer, the following ingredients are placed: 8

53 grams aluminum chloride 500 grams toluene 545 Grams of 3-methyl-3-pentene-2-one is then added through the addition funnel into the 5 liter reaction flask over a period of 5 minutes, the temperature of the mass rising to 41C. Immediately thereafter, 975 grams of 77 percent myrcene is added, with stirring, to the reaction vessel over a period of 1 hour while maintaining the temperature of the mass at 4050C. The reaction mass is then maintained at 4050C for a period of 4 /2 hours after which period 300 grams of percent phosphoric acid is added through the addition funnel. The reaction mass is then heated to l 15C and maintained at that temperature for a period of 8 hours. At the end of the reaction, the reaction mass is washed with two 1 kilo portions of 50C water; then one 250 cc portion of 50C 10 percent sodium carbonate solution; and finally one 500 gram portion of 50C 15 percent sodium sulfate solution. After separation of the organic phase from the aqueous phase, 215 grams of triethanolamine is added to the reaction mass. The 5 liter reaction vessel is then equipped with stirrer, reflux condenser, thermometer and Bidwell trap and the mass is then heated to reflux (128C) while removing solvent 165C. After 8 hours, sampling of the reaction mass and analysis thereof yielded the information that no labile organic halide is present in the reaction mass. The reaction. mass is then stripped of solvent, the crude mass weighing 1,410 grams. The crude product is rushed over and then fractionated after adding 40 grams Primol, 1 gram lonol and 10 grams calcium carbonate and purging with nitrogen, at a 1:1 reflux ratio at vapor temperature of l29131C and 2.62.9 mm Hg. pressure. Yield 845 grams.

The major task is separated out by GLC analysis in accordance with the same procedure as is set forth in Example II. The Raman spectrum for the major peak (using a Raman spectrometer manufactured by Spex Incorporated of Plainfleld, New Jersey) is, in part, set forth in FIG. 3. The Raman spectrum indicates a tetrasubstituted double bond at 1,679 cm and a carbonyl group at 1,711 cm.

The infrared analysis for the major peak is set forth in FIG. 4.

The NMR analysis for the major peak is set forth in FIG. 1.

IR, NMR and Raman spectral analyses yield the information that the resulting product is a mixture of isomers having the generic structure:

EXAMPLE VII Autoclave reaction of myrcene and 3-methyl-3-pentene-2-one thermal reaction (non-catalytic) Into a 1 liter stirred autoclave, the following ingredients are placed:

Myrcene (77%) 400 grams 2-Methyl-3-Pentene 220 grams 2-One (90%) lonol 1 gram Toluene grams product is a mixture of isomers having the generic structure:

EXAMPLE VIII Into a 2 liter reaction flask, the following materials are charged:

150 grams 275 grams Phosphoric Acid Toluene The toluene, phosphoric acid mixture is heated to C. Over a period of 15 minutes, the Diels-Alder adduct isomer mixture of Example VII is added. The cyclization reaction is carried out over a period of 5 hours at temperatures in the range of l 10l 15C. At 50C, the reaction mass is then washed with two 500 gram portions of water, one 500 gram portion of saturated sodium carbonate (to pH of 8.0) and one 15 percent solution of sodium sulfate. The toluene is then stripped off and reaction mass is rushed over at l-1.5 mm Hg. pressure and a vapor temperature of 1 10l 17C. The rushed over material is then distilled at a vapor temperature of 128-132C and a pressure of 2.5 mm Hg. (reflux ratio 9:1 GLC, NMR, IR and mass spectral analyses yield the information that the resulting product is a mixture of isomers having the generic structure:

EXAMPLE IX Preparation of oxime of l',2',3',4,5',6',7',8'-octahydro-2',3 ,8,8'-tetramethyl-2-acetonaphthone and regeneration of l,2,3 ,4,5,6',7',8'-octahydro-2',3 ,8',8 -tetramethyl-2-acetonaphthone A. Preparation of oxime In a 2 liter flask is placed 1,000 m1 of 95 percent aqueous ethanol and 61 gms. of hydroxylamine sulfate. The reaction mass is stirred while a solution of 30 gms. of sodium hydroxide in 30 gms. of water is added slowly. After an additional 35 minutes of Stirring, the reaction mass is filtered to remove the suspended sodium sulfate.

The resulting alcoholic solution of hydroxylamine is charged to a 2 liter three neck flask and gms. of material prepared as in Example V1 (prior to GLC separation) is added. The resultant mixture is stirred vigorously at reflux for approximately 8.5 hours. The solution is cooled to room temperature and the resulting crystals are filtered and air dried to give 70 gms. of oxime. The oxime is crystalized twice from toluene (23 ml toluene per gram oxime) to get 50 gms. purified oxime.

B. Regeneration of l,2,3',4,5',6,7,8'-octahydro- 2 ,3 ,8 ,8 -tetramethyl-2 -acetonaphthone A mixture of 50 gms. of the recrystalized oxime produced in Part A herein, 250 gms. of 20 percent weight/- weight sulfuric acid, and 500 gms. of 95 percent aque- 21 ous ethanol is stirred at reflux for 4.5 hours. The mixture is washed with 2,500 ml of percent sodium hydroxide solution and then with water. Toluene (100 ml) is added to the organic layer and the material is stripped under reduced pressure (IO-20 ml I-lg pressure) to remove traces of water. The washed and dried product is then distilled to give 30 gms. of product which is essentially identical to the product of Example XI by comparison of NMR spectra and GLC elution times. The NMR analysis of this material is set forth in FIG. 6.

This material is evaluated as being a very clean version of the material prepared in accordance with the process of Example VI, significantly better than the material which contains other isomers.

EXAMPLE X The Diels-Alder reaction product of Example III (250 grns. thereof) is added over a period of 50 minutes to a well stirred mixture of 1,000 gms. of toluene and 145 gms. of boron trilfuoride diethyl ether complex in a 3 liter reaction vessel equipped with stirrer, reflux condenser, thermometer, and addition funnel. The reaction mass is then maintained at 485 1C over a per- 22 thereto. In this way, a product is obtained containing geometric isomers having the basic generic structure:

EXAMPLE XI The major GLC peak of the product of Example V1 is trapped from a 500' X 0.03", SF96 (a non-polar silicone polymer manufactured by Analabs, Inc. of R0. Drawer 5397, Hamden, Connecticut 06518) column at 185C isothermal. This peak is 86.1 percent of the total material produced (according to GLC on a similar column). The trapped peak is 99.9 percent one peak when rechromatographed on a 500' X 0.03, SF96 column programmed 80l85C at 4C/min.

The trapped material is submitted for NMR analysis and the results are as follows:

0.80. doublet, J 7 cps 0.82, doublet, J 7 cps o E: H J

iod of 13 hours and is then cooled to less than C with stirring. While being maintained at 25C, 600 grns. of 10 aqueous sodium hydroxide is added to the reaction mass. The resulting organic layer is then washed with 10 percent sodium hydroxide and water. The reaction mass is then stripped of solvent thereby yielding 332 grams of crude product. The crude product is fractionated at a vapor temperature of l25l28C and a pressure of 2.2 mm Hg. after grns. of Primol, 1 gm. of Ionol and 5 grns. of calcium carbonate is added The NMR analysis is set forth in FIG. 5.

EXAMPLE XII A tobacco blend is prepared as follows:

Ingredient Parts by Weight Bright 40.1 Burley 24.9 Maryland 1.] Turkish l 1.6 Stem (flue-cured) 14.2 Glycerine 2.8

-continued Ingredient Parts by Weight Water 5.3

The following flavor formulation is prepared:

Water The above-mentioned tobacco blend is divided into four portionsz Portion A; Portion B; Portion C; and Portion D. Portion C and D are each combined separately with the above-mentioned tobacco flavor formulation, at the rate of 0.2 percent. Each of Portions A, B, C and D are then manufactured into cigarettes. The cigarettes containing tobacco Portions A and C are left as is. To the cigarettes manufactured from tobacco Portions B and D are added at the rates of 200 and 2,000 ppm the mixture of isomers of l,2,3,4',5',6,- 7,8-octahydro-2',3,8',8-tetramethyl- 2-acetonaphthone produced by the process of Example VI. The cigarettes are then evaluated by paired comparison and the results are as follows.

The aroma on smoking of cigarettes produced from tobacco Portions B and D are found to be more sweet aromatic, more woody, more green and more spicy (sandalwood, cedarwood-like) than the aroma of those cigarettes produced from Portions A and C.

In smoke flavor (main stream) the cigarettes produced from Portion D are found to be more aromatic, more sweet, more green, more bitter, woodier, slightly floral and to have a mouth coating effect.

In smoke flavor (side stream or room aroma) the cigarettes produced from Portion D are found to be more sweet, aromatic, more woody and more spicy, i.e., having an oriental, balsamic, sandalwood, cedarwood-like character.

The mixture of isomers of 1',2,3',4,5,6',7',8'- octahydro-Z ,3 ,8 ,8 '-tetramethyl-2 -acetonaphthone produced by the process of Example VI modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicy, sandalwood, cedarwoodlike character.

All cigarettes are evaluated for smoke flavor with a mm cellulose acetate filter.

EXAMPLE XIII A tobacco blend is prepared as follows:

The following flavor formulation is prepared:

The above-mentioned tobacco blend is divided into four portions: Portion A; Portion B; Portion C and For tion D. Portion C and D are each combined separately with the above-mentioned tobacco flavor formulation, at the rate of 0.45 percent. Each of Portions A, B, C and D are then manufactured into cigarettes. The cigarettes containing tobacco Portions A and C are left as is. To the cigarettes manufactured from tobacco Portions B and D are added at the rates of 600 and 1,000 ppm the mixture of isomers of l,2',3',4,5',6',7,8- octahydro-2',3',8,8-tetramethyl-2-acetonaphthone produced by the process of Example II. The cigarettes are then evaluated by paired comparison and the results are as follows.

The aroma on smoking of cigarettes produced from tobacco Portions B and D are found to be more sweet, aromatic, more woody, more green and more spicy (sandalwood, cedarwood-like) than the aroma of those cigarettes produced from Portions A and C.

The mixture of isomers of 1,2,3,4,5',6,7,8- octahydro-2 ,3 ,8 ,8 -tetramethyl-2 -acetonaphthones produced by the process of Example Il modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicy, sandalwood, cedarwoodlike character.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

When the products produced using the processes of any of Examples IV, V, VIII or IX are used in place of that of Example II, the same results are achieved as set forth above where the product of Example 11 is used. Thus, the mixture of isomers of l',2,3',4,5,6,7',8'- octahydro-2 ,3 ,8 ,8 '-tetramethyl-2 -acetonaphthones produced according to any one of the processes of Examples IV, V, VIII or IX modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicy, sandalwood, cedarwood-like character.

EXAMPLE XIV A tobacco blend is prepared as follows:

Ingredient Parts by Weight Bright 40.1 Burley 24.9

Maryland 1.1 Turkish 1 1.6 Stern (flue-cured) 14.2 Glycerine 2.8 Water 5.3

The following flavor formulation is prepared:

The above-mentioned tobacco blend is divided into four portions: Portion A; Portion B; Portion C and Portion D. Portion C and D are each combined separately with the above-mentioned tobacco flavor formulation, at the rate of 0.2 percent. Each of Portions A, B, C and C are then manufactured into cigarettes. The cigarettes containing tobacco Portions A and C are left as is. To the cigarettes manufactured from tobacco Portions B and D are added at the rates of 500 and 1500 ppm the isomer of l ,2',3,4',5',6',7',8-octahydro-2',3,8',- 8'-tetramethyl-2-acetonaphthone produced by the process of Examples VI and XI. The cigarettes are then evaluated by paired comparison and the results are as follows:

The isomer of l',2',3',4,5 ,6,7,8-octahydro-2,3 8,8-tetramethyl-2'-acetonaphthones produced by the process of Examples VI and XI modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicy, sandalwood, cedarwood-like character.

What is claimed is:

l. A tobacco product comprising tobacco, said product having added thereto an amount of from l2,000 ppm and sufficient to alter the flavor or aroma of the tobacco product of an organoleptic-property-altering composition containing a major proportion of l',2',3,- 4',5 ',6',7 ,8 '-octahydro-2 ,3 ,8 ,8 -tetramethylacetonaphthone isomers produced by a process comprising the steps of:

i. Admixing at a temperature of from about 0C up to 5 about 50C myrcene and 3-methyl-3-pentene- 2-one in the presence of a Lewis acid catalyst thereby forming a acetyl substituted cyclohexene mixture, and ii. Cyclizing the resulting acetyl substituted cyclohexene mixture with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron triflouride, and iii. Obtaining a distillation fraction having a boiling point of l29l 3 1C at a pressure of about 2.6-2.9 mm of mercury. 2. A tobacco product comprising tobacco, said prodj uct having added thereto an amount of from 1002,000 ppm and sufficient to alter the flavor or aroma of the tobacco product of a composition consisting essentially of a compound having the structure:

3. A process for altering the organoleptic properties of tobacco comprising the step of adding to tobacco a tobacco flavoring composition comprising containing a major proportion of l,2',3,4',5,6,7',8'-octahydro- 2',3,8,8-tetramethyl-acetonapthone isomers comprising the steps of:

i. Admixing at a temperature of from about 0C up to about 50C myrcene and 3-methyl-3-pentene- 2-one in the presence of a Lewis acid catalyst thereby forming an acetyl substituted cyclohexene mixture, and

ii. Cyclizing the resulting acetyl substituted cyclohexene mixture with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron trifluoride, and

iii. Obtaining a distillation fraction having boiling point of l29l 3 1C at a pressure of about 2.6-2.9 mm of mercury,

and at least one tobacco flavoring additive selected from the group consisting of:

Esters;

Aldehydes;

Ketones;

Acetals;

Natural Oils and Extracts;

Lactones and Ethers.

Claims

1. A TOBACCO PRODUCT COMPRING TOBACCO, SAID PROCUCT HAVING ADDED THERETO AN AMOUNT OF FROM 100-2,000 PPM AND SUFFICIENT TO ALTER THE FLAVOR OR AROMA OF THE TOBACCO PRODUCT OF AN ORGANOLEPTIC-PROPERTY-ALTERING COMPOSITION COMTAINING A MAJOR PROPORTION OF 1,'' 2,'' 3,'' 4,'' 5'', 6'', 7'', 8'', -OCTAHYDRO2'',3'', 8'',8'',-TETRAMETHYL-ACETONAPHTHONE ISOMERS PRODUCED BY A PROCESS COMPRISING THE STEPS OF: I. ADMIXING AT A TEMPERATURE OF FROM ABOUT 0*C UP TO ABOUT 50*C MYRCENE AND 3-METHYL-3PENTENE-2-ONE IN THE PRESENCE OF A LEWIS ACID CATALYST THEREBY FORMING A ACETYL SUBSITUTED CYCLOHEXENE MIXTURE, AND

2. A tobacco product comprising tobacco, said product having added thereto an amount of from 100-2,000 ppm and sufficient to alter the flavor or aroma of the tobacco product of a composition consisting essentially of a compound having the structure:

3. A process for altering the organoleptic properties of tobacco comprising the step of adding to tobacco a tobacco flavoring composition comprising containing a major proportion of 1'',2'',3'',4'',5'',6'',7'',8''-octahydro-2'',3'',8'',8''-tetramethyl-acetonapthone isomers comprising the steps of: i. Admixing at a temperature of from about 0*C up to about 50*C myrcene and 3-methyl-3-pentene-2-one in the presence of a Lewis acid catalyst thereby forming an acetyl substituted cyclohexene mixture, and ii. Cyclizing the resulting acetyl substituted cyclohexene mixture with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron trifluoride, and iii. Obtaining a distillation fraction having boiling point of 129*-131*C at a pressure of about 2.6-2.9 mm of mercury, and at least one tobacco flavoring additive selected from the group consisting of: Esters; Aldehydes; Ketones; Acetals; Natural Oils and Extracts; Lactones and Ethers.